Magnetic Iron Oxide Nanoparticles Coated by Coumarin-Bound Copolymer for Enhanced Magneto- and Photothermal Heating and Luminescent Thermometry.

In this work, we report on the synthesis and investigation of new hybrid multifunctional iron oxide nanoparticles (IONPs) coated by coumarin-bound copolymer, which combine magneto- or photothermal heating with luminescent thermometry. A series of amphiphilic block copolymers, including Coum-C11-PPhOx27-PMOx59 and Coum-C11-PButOx8-PMOx42 bearing luminescent and photodimerizable coumarin moiety, as well as coumarin-free PPhOx27-PMOx57, were evaluated for their utility as luminescent thermometers and for encapsulating spherical 26 nm IONPs. The obtained IONP@Coum-C11-PPhOx27-PMOx59 nano-objects are perfectly dispersible in water and able to provide macroscopic heating remotely triggered by an alternating current magnetic field (AMF) with a specific absorption rate (SAR) value of 240 W.g-1 or laser irradiation with a photothermal conversion efficiency of η = 68%. On the other hand, they exhibit temperature-dependent emission of coumarin offering the function of luminescent thermometer, which operates in the visible region between 20 °C and 60 °C in water displaying a maximal relative thermal sensitivity (Sr) of 1.53%·°C-1 at 60 °C.

Selective Water Pore Recognition and Transport through Self-Assembled Alkyl-Ureido-Trianglamine Artificial Water Channels.

In nature, aquaporins (AQPs) are proteins known for fast water transport through the membrane of living cells. Artificial water channels (AWCs) synthetic counterparts with intrinsic water permeability have been developed with the hope of mimicking the performances and the natural functions of AQPs. Highly selective AWCs are needed, and the design of selectivity filters for water is of tremendous importance. Herein, we report the use of self-assembled trianglamine macrocycles acting as AWCs in lipid bilayer membranes that are able to transport water with steric restriction along biomimetic H-bonding-decorated pores conferring selective binding filters for water. Trianglamine [(±)Δ, (mixture of diastereoisomers) and (R,R)3Δ and (S,S)3Δ], trianglamine hydrochloride (Δ.HCl), and alkyl-ureido trianglamines (n = 4, 6, 8, and 12) [(±)ΔC4, (±)ΔC8, (±)ΔC6, and (±)ΔC12] were synthesized for the studies presented here. The single-crystal X-ray structures confirmed that trianglamines form a tubular superstructure in the solid state. The water translocation is controlled via successive selective H-bonding pores (a diameter of 3 Å) and highly permeable hydrophobic vestibules (a diameter of 5 Å). The self-assembled alkyl-ureido-trianglamines achieve a single-channel permeability of 108 water molecules/second/channel, which is within 1 order of magnitude lower than AQPs with good ability to sterically reject ions and preventing the proton transport. Trianglamines present potential for engineering membranes for water purification and separation technologies.

A facile approach to modify cellulose nanocrystal for the adsorption of perfluorooctanoic acid.

Cellulose-based materials are a sustainable alternative to polymers derived from petroleum. Cellulose nanocrystal (CNC) is a biopolymer belonging to this family; it is commonly known for its important physical and chemical properties and ability to form a film. Modifying CNC via electrostatic interaction provided by cationic polymers is a facile and promising technique to enlarge the application of CNC. Herein, we report the preparation of films, from blends of negatively charged CNC and positively charged poly (trimethyl aminoethyl methacrylate) (PTMAEMA). The interaction between CNC and PTMAEMA was verified by using a quartz crystal microbalance with dissipation monitoring (QCM-D), as well as by measuring the particle size and ζ-potential of the casting mixture. To favor the application of the nanocomposite film in water treatment, the film was supported on Whatman™ paper, and adsorption tests were conducted using perfluorooctanoic acid (PFOA) as a model compound for the family of persistent fluorinated pollutants known as PFAS (per- and polyfluoroalkyl substances).

Novel Biocompatible Trianglamine Networks for Efficient Iodine Capture.

Herein, we report for the first time a biocompatible cross-linked trianglamine (Δ) network for the efficient iodine removal from the vapor phase, water, and seawater. In the vapor phase, the cross-linked network could capture 6 g g-1 of iodine, ranking among the most performant materials for iodine vapor capture. In the liquid phase, this cross-linked network is also capable of capturing iodine at high rates from aqueous media (water and seawater). This network displayed fast adsorption kinetics, and they are fully recyclable. This study reveals the high affinity of iodine for the intrinsic cavity of the trianglamine. The synthesized materials are extremely interesting since they are environmentally friendly and inexpensive and the synthesis could easily be scaled up to be used as the material of choice in response to accidents in the nuclear industry.

Synthesis and Self-Assembly of UV-Cross-Linkable Amphiphilic Polyoxazoline Block Copolymers: Importance of Multitechnique Characterization.

In the nanomedicine field, there is a need to widen the availability of nanovectors to compensate for the increasingly reported side effects of poly(ethene glycol). Nanovectors enabling cross-linking can further optimize drug delivery. Cross-linkable polyoxazolines are therefore relevant candidates to address these two points. Here we present the synthesis of coumarin-functionalized poly(2-alkyl-2-oxazoline) block copolymers, namely, poly(2-methyl-2-oxazoline)-block-poly(2-phenyl-2-oxazoline) and poly(2-methyl-2-oxazoline)-block-poly(2-butyl-2-oxazoline). The hydrophilic ratio and molecular weights were varied in order to obtain a range of possible behaviors. Their self-assembly after nanoprecipitation or film rehydration was examined. The resulting nano-objects were fully characterized by transmission electron microscopy (TEM), cryo-TEM, multiple-angle dynamic and static light scattering. In most cases, the formation of polymer micelles was observed, as well as, in some cases, aggregates, which made characterization more difficult. Cross-linking was performed under UV illumination in the presence of a coumarin-bearing cross-linker based on polymethacrylate derivatives. Addition of the photo-cross-linker and cross-linking resulted in better-defined objects with improved stability in most cases.

Polyoxazoline hydrogels fabricated by stereolithography.

The development of hydrogel materials in additive manufacturing displaying stiff and strong mechanical properties while maintaining high water uptake remains a great challenge. Taking advantage of the versatility of poly(oxazoline) (POx) chemistry and properties, we investigated in this article a new generation of POx hydrogels fabricated by stereolithography (SLA). A large range of photosensitive poly(2-methyl-2-oxazoline) resins were synthesized as hydrogel precursors for SLA photofabrication. Functionalization has been performed by direct di-methacrylation of POx terminal groups (MA2POxn) or by multi-methacrylation of poly(ethyleneimine) (PEI) units resulting from partial POx hydrolysis (MAmPOxn-PEIp). The length and the functionality of these UV-active macro-crosslinkers influence both the mechanical properties and the hydration behavior of the resulting hydrogels. The benefit of the layer-by-layer crosslinking of the POx resin during the vat photopolymerization allowed the fabrication of complex and well-defined 3D objects. The high-definition and high mechanical strength of these copolymers allow the fabrication of stiff and strong 3D hydrogels. The cytocompatibility test of the POx derivatives was conducted in solution and once the cells are encapsulated within 3D hydrogels. Finally, porous 3D scaffolds with gyroid architectures were built which provide opportunities for POx materials in tissue engineering applications.